Oil- and water-repellent compositions



United States Patent 3,378,609 OIL- AND WATER-REPELLENT QUMPGSITPUNSRoss Wade Fasick, Wilmington, Rulon Edward Johnson, Jr., Newark, andStuart Raynolds, Wiirnington, Del., assignors to E. I. du Pont deNemours and Company, Wilmington, Del., a corporation of Delaware NoDrawing. Continuation-in-part of application Ser. No. 107,330, May 3,1961. This application June 19, 1963, Ser. No. 288,894

6 Claims. (Cl. 260-090) ABSTRACT OF THE DISCLOSURE An oilandwater-repellent composition consisting essentially of (1) either apolymer of or a copolymer of CH -(XCH )CO CH CH C P and a vinyl monomerfree of non-vinylic fluorine and 2) either a polymer of a monovinylmonomer free of nonvinylic fluorine or a non-fluorinated conjugateddiene. The compositions impart oiland Water-repellent properties tofabrics when the fabrics are treated with compositions in an aqueousbath.

This application is a continuation-in-part application of applicantsprior application Ser. No. 107,330, filed May 3, 1961, now abandoned.

This invention is directed to the use of mixtures of fluorine containingpolymers and nonfluorine containing polymers as Water and oil repellentsfor textiles, paper, leather and other fibrous and porous materialswhich will absorb and transport low surface tension liquids either ontheir surfaces or into their interstices by capillary action.

Although fluorine containing polymers are readily available, it is wellknown that they are somewhat expensive. Their expense has been theprimary reason for their lack of widespread commercial acceptance.

It is, therefore, an object of this invention to provide novel water andoil repellent compositions for textiles, leather, paper and othermaterials as above described, which compositions consist of mixtures offluorine containing compounds and nonfiuorine containing compounds wherethe latter type forms a major proportion of the mixture, which arestable to heat and light, nondiscoloring, durable on substrates and inlatex form.

Another object of this invention is to provide a process for treatingtextiles, paper, leather and other materials as above described withthese compositions to render them oil and water repellent.

These and other objects will become apparent in the followingdescription and claims.

The present invention is directed to a polymeric product comprising fromabout 3% to about 60% by weight of a polymer prepared from at least onepolymerizable fluorine containing aliphatic compound of structure CO CHCH C F 1 wherein n is an integer of from 3 to 14 and from about 40% toabout 97% by weight of a polymer prepared from at least onepolymerizable vinyl compound chosen from 1 3,378,609 Patented Apr. 16,1968 ice CH CR'CONHCH OH, 1,3-butadiene, 2-chlorobutadione2,3-dichloro-1,3-butadiene or isoprene wherein R is H or methyl, R is asaturated alltyl group containing from one to 18 carbons, R is phenyl oralkyl substituted phenyl, R is hydrogen or saturated alkyl groups of oneto six carbons and Y is fluorine, chlorine or bromine; a waterdispersion or latex of this composition and fabrics or paper treatedwith this composition to render them water and oil repellent.

Another embodiment of the present invention is a polymeric compositionwhich is a mixture of (a) at least one copolymer comprising from about25% to about 99% by weight of at least one polymerizable fluorinecontaining compound cn cxcu )co cH cH c F and from 1% to about by weightof at least one polymerizable vinyl compound and (b) a polymer preparedfrom at least one polymerizable vinyl compound, the weight proportion ofsaid copolymer and said vinyl polymer being such that the mixturecontains at least 3% by weight of the component.

a water dispersion or latex of said composition and fabrics, paper andother fibrous or porous materials as above described treated with saidcomposition to render them oil and water repellent.

This invention also is directed to a process for treating fibrous orporous materials for the purpose of imparting oil and water repellencythereto which comprises impregnating said materials with an aqueous bathcontaining from about 0.1 to about 10% by weight of a composition asdefined and, by any convenient means, expressing the excess liquidtherefrom to effect a dry pick-up of between 0.1 and 10% on weight offabric of total solids, said pick-up being equivalent to at least about0.03% on weight of fabric of the fiuorinated monomer, and heating theexpressed material at from about C. to about C. for at least 15 seconds.

The present invention contemplates the methacrylate monomers It alsocontemplates the homopolymers of this type of monomer having therecurring unit ill. 1

It is to be understood that it may be the same or different in thevarious recurring units contained in the polymer chain. Thus, thepolymer can be a homopolymer of, for example, C F CH CH O CC(CH )=CH acopolymer Of C(5F13CII2CH202CC(CH3):-CH2 and fication with methacrylicacid or trans esterification with alkyl methacrylates, i.e.

The alcohols C F CH CH OH can also be esterifled by reaction withmethacrylyl chloride. An alternate meth d of preparing these esters isreaction (3) which follows:

The iodides C F CH CH I are prepared by reacting C F with ethylene (seeHaszeldine et al., J. Chem. Soc., 1949, 2856; 1950, 3041 and Park etal., Wadc 56- 590, part II, ASTIA 151014; J. Org. Chem., 23, 1166(1958)). The iodides C F I are available by the methods of Haszeldine etal. (Nature, 167, 139 (1951); J. Chem. Soc., 1953, 3761) and Brice andSimons (J.A.C.S. 73, 4016 (1951)). The alcohols are known, see Pierce etal., J'.A.C.S. 75, 5618 (1953); Park et al., J. Org. Chem, 23, 1166(1958). The method used by Pierce et al. and Park et al. to preparethese alcohols is as follows:

Another route discovered for preparing these alcohols involves thefollowing steps:

CHFZUHCIDCHQOH The polymers of these methacrylate monomers are readilyprepared using bulk, solution, suspension and emulsion techniques.Initiation can be accomplished by any of the known art methods commonlyemployed for methacrylate polymerizations.

Although the polymers of this invention can be used alone as water andoil repellents, it has been found far more advantageous to use thesepolymers as mixtures with polymers of nonfluorine containing monomers.The advantage gained is that relatively small amounts of the fluorinecontaining methacrylate polymer can be used with major amounts of theother cheaper polymer with results that are actually superior to thefluorinated polymers or mixtures of these with other polymers areapplied to substrates by essentially standard techniques which are wellknown to the art.

The fluorine containing monomers utilized according to the presentinvention have the structure CH =C (CH CO CH CH C F +1 and contain apolyfluoroalkyl group l'(CF wherein n is from 3 to about 14. When n isone or two, good repellencies are not obtained. When n is greater thanabout 14, the polymeric products become less useful since they are notreadily polymerized and serve no useful purpose over those wherein n is14 or less. The preferred species are 1H,1H,2H,2H-nonafluorohexylmethacrylate, lI-LlI-LZH, ZH-tridecafluorooctyl methacrylate,1H,1H,2H,2H,-heptadecafluorodecyl methacrylate and1H,1H,2H,2H-henic0safluorododecyl methacrylate.

The polymerizable vinyl compounds which may be used in this inventioninclude alkyl acrylates and methacrylates, vinyl esters of aliphaticacids, styrene and alkyl styrenes, vinyl halides, vinylidene halides,allyl esters, vinyl alkyl ketones, certain acrylamides and 1,3-butadiene and its derivatives. Representative examples include: methylacrylate and methacrylate, propyl acrylate and methacrylate, butylacrylate and methacrylate, isoamyl acrylate and methacrylate,2-ethylhexyl acrylate and methacrylate, octyl acrylate and methacrylate,octadecyl acrylate and methacrylate, lauryl acrylate and methacrylate,cetyl acrylate and methacrylate, N,N-diethylaminoethyl acrylate andmethacrylate, vinyl acetate, vinyl propionate, vinyl caprylate, vinyllaurate and vinyl stearate, styrene, nt-methylstyrene, p-methyl styrene,vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride,vinylidene chloride, allyl heptanoate, allyl acetate, allyl caprylate,allyl caproate, vinyl methyl ketone, vinyl ethyl ketone, 1,3-butadiene,2-chloro-l,3-butadiene, 2,3-dichlorol,3-butadiene, isoprene, N-methylolacrylamide, N-methylol methacrylamide, glycidyl acrylate and glycidylmethacrylate.

The preferred nonfluorinated monomer class is alkyl methacrylates. It isoften preferable to include a small amount of N-methylol acrylamide as acopolymer with the alkyl methacrylates since durability is increasedthereby. The preferred a kyl methacrylates are n-butyl, n-amyl, n-hexyl,isoamyl, Z-ethylhexyl, n-heptyl and n-octyl methacrylates. Styrene,2,3-dichlo-ro-1,3-butadiene and alkyl acrylates are also quite useful inthe present invention but generally less preferably than themethacrylates.

Esters of acrylic and methacrylic acid are well known and, in manycases, commercially available materials, e.g. methyl, ethyl, butyl,Z-ethylhexyl acrylates and methyl, ethyl, butyl, isobutyl, hexyl, octyl,decyl, lauryl, stearyl, N,N-diethylaminoethyl methacrylates. All arereadily prepared by esterification of the alcohol and acid in thepresence of an acid catalyst.

Vinyl acetate, vinyl Z-ethylhexanoate and vinyl stearate arecommercially available. The others are readily prepared by reaction ofvinyl acetate with the desired acid in the presence of mineral acid orby reaction of the desired acid with acetylene in the presence of acatalyst.

Styrene, alkyl styrenes, butadiene, chlorobutadiene, dichlorobutadieneand isoprene are well known commercially available compounds. Vinyl andvinylidene halides are also well known and commercially available. Allylesters are also well known and many are commercially available, e.g.allyl caproate, allyl caprylate, allyl heptanoate, allyl isovalerate andallyl propionate. Methyl vinyl ketone is well known and commerciallyavailable. Other alkyl vinyl ketones may be prepared by the reaction ofmethyl alkyl ketones with formaldehyde in the presence of sulfuric acid.Methylol acrylamide is also commercially available.

The novel water and oil repellent compositions of this inventioncomprise a mixture of a fluorine containing polymer and a nonfluorinecontaining polymer. The fluorine containing polymer may consist of oneor more fluorine containing monomers or of one or more of the fluorinecontaining monomers copo-lymerized with a nonfluorine containingmonomer. In the latter case, the polymer consists of about 25% to about99% by weight of the fluorine containing monomers. If the fluorinecontaining polymer contains less than about 25% by weight of thefluorine containing monomer, poor repellencies (or no repellency) areobtained.

The non-fluorine containing polymer is prepared from one or more of thenon-fluorine containing monomers previously described.

It is necessary that the polymer mixture contain at least 3% by weightof the fluorine containing monomer. At lower concentrations,unsatisfactory repellencies are obtained. The upper limit of 60% placedon the fluorine containing monomer is determined by economicconsiderations. When the compositions of this invention are used toimpart oil and Water repellency to fabrics and no other adjuvants ortextile treating agents are used, 25% fluorine containin monomer is apractical upper limit and about is preferred. More than fluorinatedmonomer may be used but serves no additional useful purpose. When otheradjuvants or textile treating agents are to be used however, it ispreferable to use more than 25% fiuorin'ated monomer. In this case 60%fluorinated monomer is the practical upper limit and about fluorinatedmonomer is preferred.

There is a distinct advantage obtained when a small amount of N-methylolacrylamide is included in either the fluorinated or non-fluoridatedpolymer. The advantage is that the compositions thus obtained are moredurable on fabrics than those which do not contain these compounds.

The molecular weight of both the fluorinated and nonfluorinated polymersis not a controlling factor as useful repellents are obtained over awide range of molecular weights of both types of polymers.

It should be noted that the fluorine containing monomers defined do nothave fluorine attached to the carbon atoms of the polymerizable vinylgroup but only in the groups attached to the vinyl group. For thepurposes of this invention, monomers containing fluorine attached onlyto the carbons of the vinyl group (e g. vinyl fluoride and vinylidenefluoride) are not considered to be fluorine containing monomers.

In the practice of this invention, the fluorine containing monomer andthe nonfluorine containing monomer are polymerized separately, generallyby an emulsion polymerization technique. The latexes of the fluorinecontaining polymer and nonfluorine containing polymer are then mixedtogether in the desired proportions and applied to the substrate. Thefluorinated and nontluorinated monomers may be copolymerized andresulting latex is mixed with a nonfiuorinatcd polymer latex in thedesired proportions.

In general, the compositions of this invention may be prepared by any ofthe known techniques for emulsion polymerization of vinyl compounds. Theprocess will be carried out in a reaction vessel fitted with a stirrerand external means of either heating or cooling the charge. The monomeror monomers to be polymerized together is emulsified in a water solutionof a surface active agent to a given emulsion concentration of fromabout 5% to about Usually the temperature is raised to between 40 C. and70 C. to elfect polymerization in the presence of an added catalyst. Asuitable catalyst may be any one of the commonly known agents forinitiating the polymerization of an ethylenically unsaturated compound.These include:

2,2'-az'odiisobutyramidine dihydrochloride, 2,2-azodiisobutyronitrile,

2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) sodium peroxide,

barium peroxide,

hydrogen peroxide,

ammonium persulfate,

potassium persul-fate,

and the like. The concentration of the catalyst for the polymerizationugually is between 0.1% and 2% based on the Weight of the monomers. Thesurface active agents employed to stabilize the emulsion during itsmakeup and polymerization are anionic, cationic, or non-ionicemulsifying agents, but preferably they are the cationic or nonionictype. Representative anionic emulsifying agents are alkyl (C to C)-sodium sulfate, sodium alkyl (C to C hbenzenesulfonate, sodiumalkylnaphthalenesulfonate, the sodium salt of sulfated alkenyl (C to Cacetate,

sodium ole'ate, the sodium salt of sulfated methyl oleate, ammonium w-Hpolyfluoroalkanoate (C to C and ammonium perfluoroalkanoate. Thecationic agents that may be employed include dodecyltrimethylammon-iumacetate, trimethyltetra'decylammonium chloride,hexadecyltrimethylammonium bromide, trimethyloctade'cylammoniumchloride, (.dodecylmethylbenzyl)-trirnethylammonium chloride,benzyldodecyldimethylarnmonium chloride,N-[Z-(diethylamino)ethyl]-oleamide hydrochloride. Non-ionic surfaceactive agents that may be employed include condensation products ofethylene oxide with hexylphenol, isooctylphenol, hexadecanol, oleicacid, alk'ane(C -C )-thiol, alkyl(C -C )'amines and the like. Inaddition, small amounts of chain transfer agents may be present duringthe polymerization, such as, for example, an alkanethiol of 4 to 12carbon atoms.

Suitable substrates for the application of the compositions of thisinvention are films, fibers, yarns, fabrics, and 'articles made fromfilaments, fibers, or yarns derived from natural, modified natural, orsynthetic polymeric materials or from blends of these other fibrousmaterials and other porous materials which will absorb and transport lowsurface tension liquids either on their surfaces or in their intersticesby capillary action. Specific representative examples are cotton, silk,regenerated cellulose, nylon, fiber forming line'ar polyesters,fiber-forming polya'cryloni-trile, cellulose nitrate, cellulose acetate,ethyl cellulose, paper, fiber glass, Wood pressed or otherwise hardenedWood composites, metals, unglazed porcelain, porous concrete and thelike. Dyed and undyed cotton sateen, poplin, broadcloth, jean cloth,gabardine and the like are especially adaptable for treatment with thecompositions of this invention to provide products having a highrepellency to oil and water and being relatively unaffected by theaction of heat, air and light. Materials rendered oil andWater-repellent by the invention polymer compositions retain a portionof the original repellent When laundered and dry cleaned.

The compositions are applied preferably as an aqueous dispersion bybrushing, dipping, spraying, padding, rollcoating or by any combinationof these methods. For eX- ample, the prepared concentrated dispersion ofpolymer composition maybe used as a pad bath by diluting it with Waterto a solids content of 0.1% to 10% by Weight of the bath. The textilematerial, or paper if desired, is padded in this bath, and is then freedof excess liquid, usually by squeeze rolls, so that the dry pickup(weight of the dry polymer on fiber) is between about 0.1% and 1 0% byWeight of the fiber. The treated material is then heated at C. to C. forat least about 15 seconds to impart maximum durability of the agent onthe material. T he resulting textile material or paper will be found tobe resistant to Water and oil, and the textile material Will retain itsresistance to such agents even after many launderings and dry cleanings.The polymer may, if desired, be dispersed in liquids other than Water.

Other methods for applying the compositions include the use of solutionsin place of dispersions and stepwise deposition of the two polymers.Application from solution is carried out in the same Ways, in general,as the application of dispersions. Stepwise application involvesdeposition of the two polymers separately, usually the nonfiuorinatedpolymer first. Each polymer may be applied either as a dispersion orsolution by any of the means described and a curing step may be usedafter both steps, if desired. The cure after the second application isnecessary.

The following representative examples illustrate the present invention.

EXAMPLE I This example illustrates the preparation of alcohols ofstructure C F CH CH OH.

A mixture of 49.6 parts of l-iodoperfluoroheptane, 8.6 parts ofuninhibited vinyl acetate and 0.1 part of u it'- azobisisobutyronitrilewas heated under nitrogen at 70 80 C. for five hours. Then 4.0 parts ofl-iodoperfluoroheptane and 0.1 part of azonitrile were added and heatingwas continued for two hours (the reaction is somewhat exothermic).Excess iodide was pumped off at 60/8 mm., leaving 57.4 parts of liquidresidue (95% yield of C F CH CHIO CCH Analysis.Calculated for C H F O I:C, 22.7; H, 1.0; F, 48.9; I, 21. 8. Found: C, 24.2; H, 1.5; F, 49.1; I,20.9.

The crude iodocetate obtained (55 arts) was dissolved in 80 parts of 95%ethanol and this solution was added over a period of one hour to aslurry of 20 parts of zinc dust in 120 parts of 95% ethanol and parts ofconcentrated hydrochloric acid. Two S-part portions of hydroch'loricacid were added during the addition. The mixture was then stirred forone hour, cooled to 25 C. and diluted with 100 parts of water. The oillayer was colleoted and the aqueous layer extracted with chloroform.Distillation of the combined chloroform solution gave 39.7 parts (95%)of crude product which was then heated at 60 C. for one hour with 50parts of 10% ethanolic potassium hydroxide. The mixture was drowned inwater and extracted with chloroform which after drying over magnesiumsulfate, was distilled giving C F CH CH OH, B.P. 84 C./10 mm., 111.3164.

Analysis-Calculated for C F H O: C, 26.2; H, 1.2. Found: C, 26.4; H,1.6.

Using essentially the same procedure the following WETB prepared: C P CHCH OH, CgFqCHgCIIgOI'L C F CH CH OH, C F CH CH OH, C F CH CH OI-I,

EXAM PLE II This example illustrates the general method of preparationOf (CH3)CO2CH2CH2C F2 +1- 31.0 parts of methyl rne-thacrylate, 21.4parts of 1H,lH,2H,ZH-heptafiuoropentanol-1, 0.6 part of phenothiazineand 1. 1 parts of concentrated sulfuric acid were charged into a reactorfitted with a nitrogen inlet, a stirrer, a thermometer and ahelices-packed distillation column topped by a fractionation head whichcarefully controlled the reflux ratio. The mixture was agitated undernitrogen and heated to 100 C. The reflux ratio was adjusted so that thehead temperature did not exceed 90 C. The composition of the distillate(methanol and methyl methacrylate) and reaction mixture was followed bygas chromatography. Conversion was 90% in 6-7 hours. The reactionmixture was then cooled and washed with 100 part portions of water untilacid free. Fractionation of the mixture gave 24 parts (85% yield) oflI-L lH,2H, 2H-heptafluoropentyl methacrylate,

B.-P. 66'68 C./ mm., 11 1.3566.

Analysis.Calculated for C H H O C, 38.3; H, 3.19; F, 47.1. Found: C,38.7; H, 3.20; F, 47.0.

Using the same procedure, the following other esters were prepared:

CF '(OF CH CH O CCXCHQ CH B.P. 57-58 C./0.4 mm. r2 1.3438.

CF (OF CH CH O CC(CH CH B.P. 6070 C./0.1 mm., 11 1.3412.

C./5 mm., n 1.3530.

CF (CF CH CH O CC(CH CH B.P. 60-63" C./l.0 mm., 71 1.3465.

CF (OF CH CH O CC(CH CH B.P. 95100 C./0.1 mm., M.P. 4650 C. (wax-like).

CF (OF ,CH CH O CCH CH Bl. 60 61 C./ .10 mm., n 1.3370.

8 EXAMPLE III The polymerization was run at C. for six hours with thefollowing recipe added in order shown:

Parts Water 30.0 Trimethyloctadecylammonium bromide 1.0

1H,1H,2H,2H-heptadecafluorodecyl methacrylate 10.0 Acetone 5.0Azodiisobutyramidine dihydrochloride 0.2

The solids content of the resulting latex was about 20%.

The other polymers described hereinafter, both fluorinated andnonfluorinated, were prepared using the same procedure.

EXAMPLE IV This example illustrates the general technique for evaluatingfor oil and water repellency. This procedure was used in all thefollowing examples unless otherwise noted.

A sample of the latex of poly(1i-I,1H,2H,2H-heptadecafluorodecylmethacrylate) obtained in Example HI was divided into two portions. Oneportion was diluted with water to 0.6% solids, the other portion to 0.2%solids. These two latexes were padded onto samples of fabrics (8 inchesby 8 inches) by dipping and passing through a squeeze roll adjusted sothat the squeezed fabric contained its own weight of latex wet pick-up).The fabric samples were then air dried for at least 45 minutes and thenoven cured for two to three minutes at C.

The treated fabric samples were tested for water repellency usingA.A.T.C.C. Standard Test Method 221952 of the American Association ofTextile Chemists and Colourists. A rating of 100 denotes no waterpenetration or surface adhesion, a rating of 90 denotes slight randomsticking or wetting and so on.

The oil repellency test comprises placing a drop of test solutioncarefully on the textile on a flat horizontal surface. After twominutes, any penetration or wicking into the fabric is noted visually. To aid in the observation, the test solutions contained a small amount ofoil-soluble blue dye to increase visibility. The nature of the testsolutions is shown below; Nujol of course is a purified petroleum oil.Anything with a rating of five or greater is good or excellent, anythingwith a rating of one or over can be used for certain purposes. As anexample, if a treated fabric repels the No. 16 solutions but not thenumber 7 solution, its rating is 6.

Oil Repeh Test Solution Surface Tension, lcncy Rating dynes/cm. at 25 C.

l n-Hexane" 19.2 n-Heptane 20. 0 n-Octanc 21. 8

n-Deoane 23.5

5 n-Dodeeane 2 25. 0 4 n-Tetradecane 2G. 7 27. 3 28. 7 31. 2

The results are:

Percent Fluorinated Poly (CEF[7CII2CH202CC(OI'I3) =CH2) Polymer OWF OilWater EXAMPLE V these latexes to obtain 100% wet pick-up, air dried forat least 45 minutes and then oven cured for two to three minutes at 175C. with the results shown in the table which follows. Other polymer andcopolymer mixtures I11 columns I and II, as heretofore described, thedesignations (c) and d) reflect copolymer and mixture of homopolymers,respectively.

Columns III and IV" of this table represent the loading percent onweight of fabric (percent OWF) and the percent of fluorinated monomer onthe weight of the polymer solid (head of columns-percent OWPA) with oiland water repellency figures, respectively.

TABLE I II III 20 10 7 5 Oil H10 011 H 011 H10 011 H20 Oil H10 E 3 7 1007 100 7 100 7 100 7 70 1 3 90 3 so 2 70 1 50 1 50 H 3 7 90 7 90 7 so 7 770 1 5 90 5 so 5 so 5 70 2 50 K 3 7 so 7 7 s0 6 70 4 50 1 4 70 2 70 2 701 50 1 50 M 3 s s 90 s 70 6 70 3 50 1 5 90 5 70 3 70 1 50 1 50 N 3 s 100s 100 s 90 7 70 5 50 1 6 100 6 100 3 70 2 50 1 50 were prepared, appliedand tested as previously described. EXAMPLE VI The results are alsoshown in the following table.

In the table which follows, columns I and II, with numerical and capitalletter designation, represent fluorinated and non-fluorinatedcompositions, respectively, as follows:

I II

CH =CHNHCHaOH 4% Percent Fluorinatod Poly (C7F15CI'T2CIIZOQCC (CH3) CH2)Polymer OWF Oil Water In the same manner as above, the other two samplesof cloth were treated with 0.6% and 0.2% solutions ofpoly(1H,lH,2H,2H-pentadecailuorononyl acrylate) in the same solventmixture. After drying and curing as heretofore described, the followingresults were obtained.

Percent Fluorinated Poly (C'IF15CIIQCI11L)2C C H C H2) Polymer OWF OilVat or In the same manner as the above examples the polymers andcopolymer mixtures described above are applied to other textiles such aswool, polyethylene terephthalate polyacrylonitrile, nylon and the likewith comparable results. The same method of application, in principle,is used for application to leather and the like. For application topaper, the same methods may also be used, or more conveniently, thecompositions may be added to the beater stock wherein it becomesincorporated into the paper; the usual drying step of paper manufacturebeing sutficient to cure the polymer composition to the paper. The samemethods of application of the polymer and copolyiner mixtures can beused for wood, wood products, metals and other porous materials. Thecuring step of heating to l65195 C. is needed in all cases. In the caseof treated metals, cetane Contact angles of 80 or higher are obtained.

The preceding examples illustrate the preparation of the compositions ofthis invention and their use for rendering textile fabrics and othersubstrates oil and water repellent when no other adjuvants or textiletreating agents are used. As noted hereinbefore, it is common practicein the textile industry to treat fabrics with several agents at the sametime. These agents may include softeners, crease resistance agents,wetting agents, antistatic agents, resin finishes and the like. Many ofthese agents tend to dilute the vinyl polymer portion of the presentpolymer composition with material which are inert as oil and waterrepellents. In such cases better results are obtained it higherconcentrations of fiuorinated polymers prepared from are used than whenthe oil and water repellent compositions of this invention are usedalone. As indicated earlier, when other adjuvants are not used about 25%by weight fiuorinated polymer in the polymer composition is thepractical upper limit. Greater concentrations serve no useful purposeand increase cost. When other adjuvants are present up to about 60% byweight fluorinated polymer gives useful results, but about 60% is thepractical upper limit. About 40% by weight fiuorinated polymer ispreferred in such cases, particularly from a value in use viewpoint. Itshould be understood that oil and water repellency may still beobtained, although not improved, if more than about 60% fluorinatedpolymer is used. Indeed, high oil and water repellency can be obtainedusing as high as 95% fiuorinated polymer. Examples VII and VIII whichfollow illustrate the use of higher concentrations of fluorinatedpolymer associated with textile treating baths containing otheradjuvants than the oil and water repellent compositions of thisinvention.

12 EXAMPLE v11 Following the procedure of Example II, polymers wereprepared according to each of the following recipes.

A. Fluorinated polymer Parts Water 2,200 Fluorinated monomer 1,000n-Butyl aerylate 20 N-met'hylolacrylamide as 60% aqueous solution 5Dimethyloctadecylamine 30 Glacial acetic acid 18.3 Acetone 791Azodiisobutyramidine dihydrochloride 0.4

1 The monomer was CI'IE C(CII3)CO2CLI2C IB(CF2)X1F \Vlth 11:6, S and 10in the relative proportions 312:1, respectively, and also small amountsof 11:12 and 14.

The mixture was heated at 60 C. for four hours. The resulting emulsionwas used in Example VIII below.

B. N on-fluorinatecl monomer Parts Water 2,200 2-ethylhexyl methacrylate1,000 N-methylolacrylamide as 60% aqueous solution l8Dimethyloctadecylamine 20 Glacial acetic acid 12.2 Sodium chloride 0.7Acetone 237 Azodiisobutyramidine dihydrochloride 0.222

The mixture was heated at C. for four hours. The resulting emulsion wasused in Example VIII below.

EXAMPLE VIII Percent Water To make 100Nonylphenoxypoly(ethyleneoxy)ethanol (Igepal 630-Antara) 0.04

Tartaric acid 0.04

Aqueous dispersion of polyethylene (Protolu-b PE- Proctor Chemical Co.)1.50 Resin finish for cotton (Aerotex 23American Cyanamid) 5.00Magnesium chloride 0.50 Phobotex 1.083, 2.500, 3.333 Polymer mixture3.333, 4.167

1 Phobotex is a mixture of 25% wax and the acetate derivative preparedfrom hexamethylolmelamine, stearic acid and triethanolainine asdescribed in U.S. Patent No. 2,783, 23lCiba.

Samples of cotton poplin and 50:50 cotton-Dacron blend (Dacron is DuPonts trade name for polyethylene terephthalate fiber) were padded witheach of the pad baths to obtain 60% wet pick-up, following the generalprocedure of Example V. After curing as described in Example V, eachtreated fabric sample was evaluated for oil and water repellency.Portions of each fabric sample were then given three standard washingsand other portions three standard dry cleanings. These portions werethen evaluated for oil and water repellency. All repellencies wereobtained as in Example IV. The results are shown in the table below. Inthe table, Column I gives the amount of fluorinated polymer in thepolymer mixture with nonfluorinated polymer on the weight of polymersolids (OWPS). In the column headed Loading, OWF means on the weight offabric and Polymer refers to the mixture of fluorinated andnonfiuorinated polymers.

A standard washing consists of immersing the fabric 13 sample for 15minutes with agitation in water at 7080 C. containing 0.2% by weightheavy duty, built detergent (Tide), rinsing in boiling water, then coldwater and ironing at 235 F. A standard dry cleaning consists ofagitating the fabric sample for 20 minutes with tetrachloroethylenecontaining 2.5% by weight commercial 14 dry cleaning detergent (R. R.Street Co.) and 0.5% water at 80 F. and then drying and ironing 235 F.

The results in the table show that in the formulations used, mixtures ofnonfluorinated and fluorinated polymers containing up to 60% fluorinatedpolymer are useful oil and water repellents.

TAB LE I Loading, percent OWF Repellencies Cotton Poplin Initial 3 SW 3SD 2 OWPS Polymer Phobotex Oil Water Oil Water Oil Water 1 After 3standard washings. After 3 standard dry cleanings.

TAB LE I Loading, percent OWF Repellencies Cotton-"Dacron Blend 50:50

Initial 3 SW 8 SD 2 OWPS Polymer Phobotex Oil Water Oil Water Oil Water1 After 3 standard w ashlngs.

2 After 3 stenda dcy rleanings.

It is understood that the preceding examples may be varied, within thescope of the total specification as understood by those skilled in theart, to achieve substantially the same results.

As many widely different embodiments of this invention may be madewithout departing from the spirit-and scope thereof, it is to beunderstood that this invention is not limited to the specificembodiments thereof except as defined in the appended claims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A polymeric composition consisting essentially of (1) from about 3%to about 60% by Weight of a polymer consisting of units derived from atleast one polymerizable compound of the structure wherein n has a valueof from 3 to 14; and the balance being essentially (2) from about 97% toabout 40% by weight of a polymer consisting of units derived from atleast one polymerizable compound selected from the group consisting of(a) monovinyl compounds free of nonvinylic fluorine, and (b)nonfluorinated conjugated dienes.

2. The polymeric composition of claim 1 wherein the polymer defined inpart (2) is selected from the g oup consisting of R1 CHz=( 3OO R CH =CHOCR CH =CHR CH =CHY, CH =CY CH =CHCH O CR CH3 CH2=CH-(I%R,CH2=!:C02CH2OH2NR 2 CH =CR CONHCH OH, 1,3-butadien, Z-chlorobutadiene,2,3-dichloro-1,3-butadiene and isoprene; wherein R is H or methyl, R isa saturated alkyl group containing from one to 18 carbons, R is phenylor alkyl-substituted phenyl, R is hydrogen or saturated alkyl groups ofone to six carbons and Y is fluorine, chlorine or bromine.

3. A polymeric composition consisting essentially of (1) a copolymerconsisting of (a) from about to about 99% by Weight of units derivedfrom at least one polymerizable fluorine-containing compound of thestructure CH =C(CH )C-O CH CH C, F wherein n is from 3 to 14 and thebalance of the copolymer being essentially (b) from about 75% to about1% by weight of units derived from at least one polymerizable vinylcompound free of non-vinylic fluorine, and

(2) a vinyl polymer consisting of units derived from at least onepolymerizable compound selected from the group consisting of (a)mono-vinyl compounds free of non-vinylic fluorine, and (b)nonfluorinated conjugated dienes, the weight proportion of saidcopolymer and said vinyl polymer being such that the mixture containsfrom 3% to by weight of units derived from said polymerizablefluorine-containing compound component. I

4. The polymeric composition of claim 3 wherein the polymerizable vinylcompound free of non-vinylic fluorine of part (1)(b) is selected fromthe class consisting of alkyl acrylates, alkyl methacrylates, vinylesters of aliphatic acids, styrene, alkyl styrenes, vinyl halides,vinylidene halides, alkyl esters, vinyl alkyl ketones, acrylamides, and1,3-butadiene;

and wherein the vinyl polymer of part (2) is selected from the classconsisting of R1 CH2=(IJCO2R2 CH =CHO CR CH =CHR CH CHY CH =CY CH =CHCHO CR 0 CH CHFCH(|LJR2, OHz=( )COzOH2CH2NR2 CH =CR CONHCH OH,1,3-butadiene, 2-chlorobutadiene, 2,3-dichloro-1,3-butadiene andisoprene; wherein R is H or methyl, R is a saturated alkyl groupcontaining from one to 18 carbons, R is phenyl or alkyl-substitutedphenyl, R is hydrogen or saturated alkyl groups of one to six carbonsand Y is fluorine, chlorine or bromine.

5. The polymeric composition of claim 3 wherein the units derived fromthe polymerizable vinyl com-pound free of non-vinylic fluorine of part(1)(b) are units of an alkyl acrylate and N-methylolacrylamide; and

wherein the vinyl polymer of part (2) consists of units derived from analkyl methacrylate and N-methylolacrylamide.

6. The polymeric composition of claim 5 wherein the alkyl acrylate ofpart (1)(b) is butyl acrylate; and

wherein the alkyl methacrylate of part (2) is 2-ethylhexyl methacrylate.

References Cited UNITED STATES PATENTS 2,642,416 6/1953 Ahlbrecht et a1.260-900 3,102,103 8/1963 Ahlbrecht et a1 260-296 3,277,039 10/1966Maraseia et al. 260-890 3,282,905 11/1966 Fasick et al. 260-890 MURRAYTILLMAN, Primary Examiner.

.T. L. WHITE, G. F. LEMES, Asssitant Examiners.

